CN113880063A - Aluminum removing method for ferrophosphorus slag after lithium extraction of waste lithium iron phosphate and preparation method of battery-grade ferric phosphate - Google Patents
Aluminum removing method for ferrophosphorus slag after lithium extraction of waste lithium iron phosphate and preparation method of battery-grade ferric phosphate Download PDFInfo
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Abstract
The invention relates to a method for removing aluminum from phosphorus iron slag after lithium extraction of waste lithium iron phosphate and a preparation method of battery-grade iron phosphate. The aluminum removing method comprises the following steps: mixing the ferrophosphorus slag obtained after lithium extraction of waste lithium iron phosphate, an iron simple substance, acid and water, and carrying out acid leaching reaction to obtain slurry A; mixing the slurry A with an aluminum remover to perform aluminum removal reaction, and then removing solids to obtain a phosphorus iron liquid after aluminum removal; the aluminum remover is at least one of picolinic acid compounds, quinolinecarboxylic acid compounds and isoquinoline-3-carboxylic acid compounds. The organic aluminum removing agents can be complexed with iron and aluminum to form metal organic complex precipitates with different solubilities, the solubility difference of iron and aluminum can be effectively amplified, and preferential precipitation of aluminum is guaranteed, so that aluminum impurities are effectively removed, the product purity of the iron phosphate is improved, and the high yield of the iron phosphate can be guaranteed. In addition, the aluminum removal method has the advantages of simple operation, less equipment investment, environmental protection, controllable quality and easy industrialization.
Description
Technical Field
The invention relates to the technical field of battery material recovery, in particular to a method for removing aluminum from a phosphorus iron slag after lithium extraction of waste lithium iron phosphate and a method for preparing battery-grade iron phosphate.
Background
Because the lithium iron phosphate battery has the advantages of high specific capacity, stable structure, safe performance, long service life and the like, the lithium iron phosphate battery is widely applied to the field of new energy. With the rapid development of new energy automobiles in China, the life cycle of the lithium ion battery is generally 3-5 years at present, and the scrappage of the power battery in China can reach 12-17 ten thousand tons along with the lapse of time. A large amount of retired waste power batteries are in urgent need of recovery treatment, and because the lithium iron phosphate batteries are rich in lithium and iron phosphate, the recovery of all components of lithium and iron in the retired lithium iron phosphate batteries is very important from the viewpoints of resource recycling and environmental protection.
Because the lithium iron phosphate positive electrode powder in the waste lithium iron phosphate batteries is attached to the aluminum foil, the aluminum content of the recovered lithium iron phosphate positive electrode waste is inevitably high, and the method for preparing battery-grade iron phosphate by recovering by a wet process generally faces the problem of high aluminum impurity content. In practice, the aluminum removal process mainly has two directions, the first is that the lithium iron phosphate slag is subjected to alkali leaching to remove aluminum, and the second is that the lithium iron phosphate/iron phosphate is subjected to acid leaching to obtain acid leaching solution, and then the aluminum is removed through precipitation or resin adsorption. The content of aluminum impurities in the iron phosphate prepared by alkaline leaching and aluminum removal is still generally higher than the battery grade application standard, the problem that iron and aluminum influence each other usually exists in the latter in the existing acid leaching process, the impurity removal cost is increased, and the purity and yield of the finally obtained iron phosphate product are not high. In conclusion, the existing aluminum removal process of iron phosphate has the problems of long process, poor deep aluminum removal effect, low product purity and yield and the like.
At present, a method for recovering iron phosphate from iron phosphorus slag after lithium extraction of lithium iron phosphate lithium batteries is reported, wherein inorganic acid is adopted to leach iron and phosphorus, resin is used for removing aluminum, and alkali is added to adjust the pH value of acid leaching solution to precipitate the iron phosphate. Although the process flow is simple, the aluminum removal rate is high; however, the acid dosage is large, cation impurities are introduced, the alkali dosage consumed in the pH adjustment stage is also large, the production cost is increased, the cation impurity removal difficulty is large, and the purity of the iron phosphate is low.
Also reported is a method for the hydrometallurgical regeneration of iron phosphate from waste lithium iron phosphate batteries: adding an alkali metal oxide precipitate Al (OH) into an aluminum-containing ferrous phosphate lithium pickle liquor at a pH of 3-53. The method has good deep aluminum removal effect, but because of Ksp(Fe3(PO4)2)＝1.0×10-38，Ksp(AlPO4·2H2O)＝6.9×10-19，Fe3(PO4)2Prior to AlPO4·2H2The deposition of O, the Fe is easily caused in the process of neutralizing the residual acid2+And Al3+Co-precipitation of (1), Fe2+And PO4 3-The loss of iron phosphate is large, and the recovery rate and the purity of the iron phosphate are low.
In addition, a method for removing aluminum from the waste lithium iron phosphate acidic leaching solution is also reported: will contain Al3+，Fe3+And PO4 3-Adjusting the pH value of the pickle liquor to 2.0-3.5 to ensure that 94.6-99.9 percent of Al is contained in the pickle liquor3+Filter residue is formed in the form of iron-aluminum coprecipitate, and the aluminum content of the obtained iron phosphate is lower than 0.02 percent. But due to Ksp (FePO)4·2H2O)＝1.3×10-22The ferric phosphate is easier to precipitate, and the loss rate of the ferric phosphate in the process of removing aluminum is higher than 30%. It can be seen that, in the wet recovery of the valuable metals in the lithium iron phosphate, the lithium and iron in the lithium iron phosphate are usually leached by using a leaching agent to become soluble lithium salts and iron salts, and then a precipitating agent is introduced or alkali is used for neutralization to convert the lithium ions and the iron ions into insoluble precipitates, so as to obtain separation and recovery. However, in the existing process, lithium and iron are often leached at the same time and then are separated by respective precipitation, but the operation causes the two to affect each other, which increases the cost of impurity removal, the purity of the final product is not high, and the whole recovery process is long, complicated and high in cost.
Disclosure of Invention
Based on the method, the invention provides a method for deeply removing aluminum from the ferrophosphorus slag after lithium extraction of waste lithium iron phosphate.
The technical scheme is as follows:
a method for removing aluminum from phosphorus-iron slag after lithium extraction of waste lithium iron phosphate comprises the following steps:
mixing the ferrophosphorus slag obtained after lithium extraction of waste lithium iron phosphate, an iron simple substance, acid and water, and carrying out acid leaching reaction to obtain slurry A;
mixing the slurry A with an aluminum remover to perform aluminum removal reaction, and then removing solids to obtain a phosphorus iron liquid after aluminum removal;
the aluminum remover is at least one selected from picolinic acid compounds, quinolinecarboxylic acid compounds and isoquinoline-3-carboxylic acid compounds.
In one embodiment, the picolinic acid based compound is selected from 2-picolinic acid, 3-phenyl-2-picolinic acid, methyl 2-picolinate, ethyl 2-picolinate, propyl 2-picolinate, or butyl 2-picolinate.
In one embodiment, the quinolinecarboxylic acid compound is selected from 2-quinolinecarboxylic acid, methyl 2-quinolinecarboxylate, ethyl 2-quinolinecarboxylate, propyl 2-quinolinecarboxylate, or butyl 2-quinolinecarboxylate.
In one embodiment, the isoquinoline-3-carboxylic acid compound is selected from isoquinoline-3-carboxylic acid, isoquinoline-3-carboxylic acid methyl ester, isoquinoline-3-carboxylic acid ethyl ester, isoquinoline-3-carboxylic acid propyl ester or isoquinoline-3-carboxylic acid butyl ester.
In one embodiment, the mass ratio of the aluminum removing agent to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.01-0.1): 1.
in one embodiment, the mass ratio of the elementary iron to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.15-0.35): 1.
in one embodiment, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and phosphoric acid.
In one embodiment, the mass ratio of the acid to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.5-1.5): 1.
in one embodiment, the solid-to-liquid ratio of the slurry A is 20g/L to 150 g/L.
In one embodiment, the parameters of the acid leaching reaction include:
the reaction temperature is 40-80 ℃, and the reaction time is more than or equal to 4 hours.
In one embodiment, the parameters of the aluminum removal reaction include:
the reaction temperature is 50-100 ℃, and the reaction time is more than or equal to 2 hours.
In one embodiment, the aluminum removal reaction is carried out in an inert gas, carbon dioxide or nitrogen atmosphere.
The invention also provides a preparation method of the battery-grade iron phosphate, which comprises the following steps:
preparing the ferrophosphorus solution according to the aluminum removing method of the ferrophosphorus slag after extracting lithium from the waste lithium iron phosphate;
and mixing the ferrophosphorus solution with an oxidant and a pH regulator to perform an oxidation reaction.
In one embodiment, the oxidizing agent is selected from at least one of hydrogen peroxide, air, ozone, or oxygen, and/or
The pH regulator is at least one selected from ammonia water, ammonium carbonate or ammonium bicarbonate.
In one embodiment, the mass ratio of the oxidant to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.3-0.9): 1; and/or
The parameters of the oxidation reaction include: the reaction temperature is 40-100 ℃, the reaction time is more than or equal to 4 hours, and the pH value of the reaction system is 1.5-2; and/or
After the oxidation reaction is finished, filtering, washing and drying treatment are also carried out.
The invention has the following beneficial effects:
according to the invention, through the characteristic that the picolinic acid compounds, the quinolinic acid compounds and the isoquinoline-3-formic acid compounds can be complexed with metals such as iron and aluminum to form metal organic complex precipitates with different solubilities, the solubility difference of iron and aluminum is effectively amplified, and the preferential precipitation of aluminum is ensured, so that aluminum impurities are effectively removed, the product purity of the iron phosphate is improved, and the high yield of the iron phosphate is ensured.
Tests show that the method disclosed by the invention has the advantages that the removal rate of aluminum impurities is higher than 99%, the loss rate of iron is less than 4%, and the high purity and yield of iron phosphate are ensured while deep aluminum removal is carried out.
In addition, the aluminum removal method has the advantages of simple operation, less equipment investment, environmental protection, controllable quality, easy industrialization and the like, can generate better economic and social benefits, and has wide application prospect.
Drawings
Figure 1 is an XRD pattern of the battery grade iron phosphate prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
In the present invention, "at least one" means any one, any two or more of the listed items.
The raw materials, reagents, and the like used in the following embodiments are all commercially available products unless otherwise specified.
The technical scheme of the invention is as follows:
a method for removing aluminum from phosphorus-iron slag after lithium extraction of waste lithium iron phosphate comprises the following steps:
mixing the ferrophosphorus slag obtained after lithium extraction of waste lithium iron phosphate, an iron simple substance, acid and water, and carrying out acid leaching reaction to obtain slurry A;
mixing the slurry A with an aluminum remover to perform aluminum removal reaction, and then removing solids to obtain a phosphorus iron liquid after aluminum removal;
the aluminum remover is at least one selected from picolinic acid compounds, quinolinecarboxylic acid compounds and isoquinoline-3-carboxylic acid compounds.
The picolinic acid compounds, the quinolinecarboxylic acid compounds and the isoquinoline-3-carboxylic acid compounds can be complexed with metals such as iron and aluminum to form metal organic complex precipitates with different solubilities, so that the solubility difference of iron and aluminum can be effectively amplified, and the preferential precipitation of aluminum is ensured, thereby effectively removing aluminum impurities, improving the product purity of the iron phosphate and ensuring the high yield of the iron phosphate.
In one embodiment, the picolinic acid based compound is selected from 2-picolinic acid, 3-phenyl-2-picolinic acid, methyl 2-picolinate, ethyl 2-picolinate, propyl 2-picolinate, or butyl 2-picolinate; the quinoline carboxylic acid compound is selected from 2-quinoline carboxylic acid, 2-quinoline carboxylic acid methyl ester, 2-quinoline carboxylic acid ethyl ester, 2-quinoline carboxylic acid propyl ester or 2-quinoline carboxylic acid butyl ester; the isoquinoline-3-formic acid compound is selected from isoquinoline-3-formic acid, isoquinoline-3-methyl formate, isoquinoline-3-ethyl formate, isoquinoline-3-propyl formate or isoquinoline-3-butyl formate. The compounds can be effectively complexed and precipitated with metals such as iron, aluminum and the like, the solubility difference of iron and aluminum is amplified, and the preferential precipitation of aluminum is ensured, so that aluminum impurities are effectively removed.
In one embodiment, the mass ratio of the aluminum removing agent to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.01-0.1): 1. the mass ratio in the range is more beneficial to the deep aluminum removal of the invention and simultaneously ensures higher iron phosphate purity and yield. If the adding amount of the aluminum removing agent is lower than the range of the invention, the aluminum removing efficiency is greatly reduced, so that the purity of the iron phosphate is insufficient; if the adding amount of the aluminum removing agent is higher than the range of the invention, the aluminum removing efficiency is good, but the yield of the iron phosphate is greatly reduced.
In one embodiment, the mass ratio of the elementary iron to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.15-0.35): 1. the mass ratio in the range is more beneficial to the deep aluminum removal of the invention and simultaneously ensures higher iron phosphate purity and yield.
In one embodiment, the acid is selected from at least one of hydrochloric acid, sulfuric acid, and phosphoric acid. And dissolving soluble substances in the phosphorus iron slag after lithium extraction of the waste lithium iron phosphate through the action of the inorganic strong acid.
In one embodiment, the mass ratio of the acid to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.5-1.5): 1. the mass ratio in the range is more beneficial to the deep aluminum removal of the invention and simultaneously ensures higher iron phosphate purity and yield.
In one embodiment, the solid-to-liquid ratio of the slurry A is 20g/L to 150 g/L. Likewise, the advantage of controlling the solid-to-liquid ratio ranges mentioned above is to ensure a higher iron phosphate purity and yield while ensuring deep aluminum removal.
In one embodiment, the parameters of the acid leaching reaction include:
the reaction temperature is 40-80 ℃, and the reaction time is more than or equal to 4 hours.
In one embodiment, the parameters of the aluminum removal reaction include:
the reaction temperature is 50-100 ℃, and the reaction time is more than or equal to 2 hours.
In one embodiment, the aluminum removal reaction is carried out in an inert gas (e.g., argon)Helium gas(He)、Neon gas(Ne)、Argon gas(Ar)、Krypton gas(Kr)、Xenon gas(Xe)), carbon dioxide or nitrogen. This is advantageous for improving the purity of the iron phosphate.
In one embodiment, the manner of removing the solids is by filtration.
The invention also provides a preparation method of the battery-grade iron phosphate, which comprises the following steps:
preparing the ferrophosphorus solution according to the aluminum removing method of the ferrophosphorus slag after extracting lithium from the waste lithium iron phosphate;
and mixing the ferrophosphorus solution with an oxidant and a pH regulator to perform an oxidation reaction.
In one embodiment, the oxidizing agent is selected from at least one of hydrogen peroxide, air, ozone, or oxygen.
In one embodiment, the mass ratio of the oxidant to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.3-0.9): 1.
In one embodiment, the pH adjusting agent is selected from at least one of ammonia, ammonium carbonate or ammonium bicarbonate.
In one embodiment, the parameters of the oxidation reaction include: the reaction temperature is 40-100 ℃, the reaction time is more than or equal to 4 hours, and the pH value of the reaction system is 1.5-2.
In one embodiment, after the oxidation reaction is finished, the reaction solution is further filtered, washed and dried.
The preparation method of the battery-grade iron phosphate has the advantages of simple operation, less equipment investment, environmental protection, controllable quality, easy industrialization and the like, can generate better economic and social benefits, and has wide application prospect.
The following is a further description with reference to specific examples and comparative examples.
It can be understood that the ferrophosphorus slag obtained after lithium extraction from waste lithium iron phosphate may have slightly different element components, but the aluminum removal method disclosed by the present invention is applicable to various ferrophosphorus slag obtained after lithium extraction from waste lithium iron phosphate, and for convenience of describing the present invention, the element content analysis of the ferrophosphorus slag obtained after lithium extraction from waste lithium iron phosphate used in the following examples and comparative examples is as follows:
the balance is substantially carbon and oxygen, in addition to the above elements.
Example 1
Mixing and pulping 400g of phosphorus iron slag after lithium extraction of waste lithium iron phosphate, 80g of iron powder, 2600g of pure water and 600g of 98% sulfuric acid, reacting for 4.0 hours at 80 ℃, and obtaining the Fe-containing iron after the reaction is finished2+、Al3+、PO4 3-Acid slurry a of (a).
Under the protection of carbon dioxide, 4g of 2-picolinic acid is added into the slurry A, the reaction temperature is controlled at 100 ℃, the reaction time is 2.0 hours, and after the reaction is finished, solid-liquid separation is carried out to obtain the aluminum-removed ferrophosphorus solution.
And mixing the ferrophosphorus solution with 400g of 30% hydrogen peroxide, adjusting the pH value to 1.8 by ammonia water, reacting at 100 ℃ for 4 hours, carrying out solid-liquid separation, and washing to obtain the battery-grade iron phosphate with the yield of 96.6%.
XRD (X-ray diffraction) testing is carried out on the iron phosphate obtained by the preparation method, so that a diffraction pattern shown in figure 1 is obtained, and the diffraction pattern is compared with a corresponding product standard card, so that the product obtained by the embodiment is confirmed to be the iron phosphate.
The iron phosphate prepared by the method is detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 90 ppm.
Example 2
Mixing and pulping the phosphorus iron slag obtained after extracting lithium from 700g of waste lithium iron phosphate, 245g of iron powder, 8.4kg of pure water and 1050g of 85 percent phosphoric acid, reacting for 5.0 hours at 65 ℃, and obtaining the Fe-containing iron after the reaction is finished2+、Al3+、PO4 3-Acid slurry a of (a).
Under the protection of nitrogen, 21g of isoquinoline-3-formic acid is added into the slurry A, the reaction temperature is controlled at 80 ℃, the reaction time is 3.0 hours, and after the reaction is finished, solid-liquid separation is carried out to obtain the aluminum-removed ferrophosphorus solution.
And introducing oxygen into the ferrophosphorus solution at the flow rate of 0.81L/min, controlling the oxygen partial pressure of the solution to be 1.2MPa through a pressure reducing valve, adjusting the pH value to be 2.0 by ammonium carbonate, reacting at 60 ℃ for 5 hours, then carrying out solid-liquid separation and washing to obtain the battery-grade iron phosphate, wherein the yield is 97.3%.
The iron phosphate prepared by the method is detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 60 ppm.
Example 3
Mixing 300g of ferrophosphorus slag after lithium extraction from waste lithium iron phosphate, 45g of iron powder, 6100g of pure water and 822g of 36.5 percent hydrochloric acid for size mixing, reacting for 6.0 hours at 50 ℃, and obtaining Fe-containing iron after the reaction is finished2+、Al3+、PO4 3-Acid slurry a of (a).
Under the protection of helium, 15g of 2-quinolinecarboxylic acid is added into the slurry A, the reaction temperature is controlled at 60 ℃, the reaction time is 4.5 hours, and after the reaction is finished, solid-liquid separation is carried out to obtain the aluminum-removed ferrophosphorus solution.
Mixing the ferrophosphorus solution with 800g of 30% hydrogen peroxide, adjusting the pH value to 1.5 by ammonium bicarbonate, reacting for 6 hours at 40 ℃, then carrying out solid-liquid separation and washing to obtain the battery-grade iron phosphate, wherein the yield is 96.1%.
The iron phosphate prepared by the method is detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 50 ppm.
Example 4
500g of phosphorus iron slag, 125g of iron powder, 24.7kg of pure water, 127.5g of 98 percent sulfuric acid and 147g of 85 percent phosphoric acid are mixed and slurried, the reaction is carried out for 8.0 hours at the temperature of 40 ℃, and after the reaction is finished, Fe-containing iron is obtained2+、Al3+、PO4 3-Acid slurry a of (a).
Under the protection of nitrogen, 50g of isoquinoline-3-ethyl formate is added into the slurry A, the reaction temperature is controlled at 50 ℃, the reaction time is 5 hours, and after the reaction is finished, solid-liquid separation is carried out to obtain the aluminum-removed ferrophosphorus solution.
And introducing oxygen into the ferrophosphorus solution at the flow rate of 1.09L/min, controlling the oxygen partial pressure of the solution to be 1.2MPa through a pressure reducing valve, adjusting the pH value to be 1.6 by ammonium carbonate, reacting at 80 ℃ for 4 hours, then carrying out solid-liquid separation and washing to obtain the battery-grade iron phosphate, wherein the yield is 96.8%.
The iron phosphate prepared by the method is detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 70 ppm.
Example 5
The phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate is treated according to the same steps and processes as in example 1, except that 3-phenyl-2-picolinic acid is used as an aluminum remover instead of 2-picolinic acid in the aluminum removal step, and the other operations are the same as in example 1.
The yield of iron phosphate produced was 96.1%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 40 ppm.
Example 6
The phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate is treated according to the same steps and processes as in example 1, except that 2-quinolinecarboxylic acid methyl ester is used as an aluminum remover instead of 2-picolinic acid in the aluminum removal step, and the other operations are the same as in example 1.
The yield of iron phosphate produced was 96.9%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 80 ppm.
Example 7
The phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate is treated according to the same steps and processes as in example 1, except that a mixture formed by mixing 2-propyl picolinate, 2-butyl quinolinecarboxylate and isoquinoline-3-propyl formate according to a mass ratio of 1:2:1 is used as an aluminum remover instead of 2-picolinic acid in the aluminum removal step, and the other operations are the same as in example 1.
The yield of iron phosphate produced was 96.3%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 65 ppm.
Comparative example 1
The same steps and processes as in example 4 are carried out to treat the phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate, except that octahydroxyquinoline is used as an aluminum remover instead of methyl isoquinolineformate in the aluminum removal step, and the other operations are the same as in example 4.
The yield of iron phosphate produced was 74.6%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 50 ppm.
Comparative example 2
The same steps and processes as in example 4 are carried out to treat the phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate, except that salicylic acid is used to replace methyl isoquinoline formate as an aluminum remover in the aluminum removal step, and the other operations are the same as in example 4.
The yield of iron phosphate prepared was 97.6%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 20ppm, and the content of impurity aluminum is 6320 ppm.
Comparative example 3
The same steps and processes as in example 4 are carried out to treat the ferrophosphorus slag after lithium extraction from the waste lithium iron phosphate, except that Ethylene Diamine Tetraacetic Acid (EDTA) is used as an aluminum remover instead of methyl isoquinoline formate in the aluminum removal step, and the other operations are the same as in example 4.
The yield of iron phosphate produced was 76.3%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 35ppm, and the content of impurity aluminum is 5860 ppm.
Comparative example 4
The same steps and processes as in example 4 are carried out to treat the phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate, except that hydroxyethylidene diphosphonic acid (HEDP) is used as an aluminum remover instead of methyl isoquinoline formate in the aluminum removal step, and the other operations are the same as in example 4.
The yield of iron phosphate produced was 72.5%. Detected by atomic emission spectrometry (ICP), the contents of impurities of sodium, magnesium, silicon, sulfur, potassium, calcium, chromium, cobalt, nickel, manganese, zinc, cadmium and lead are all less than 30ppm, and the content of impurity aluminum is 5920 ppm.
And (4) analyzing results:
as can be seen from the results of example 4 and comparative example 1, in the step of comparative example 1, octahydroxyquinoline is used as an aluminum remover, although the content of aluminum ion impurities is greatly reduced (50ppm), the yield of iron phosphate is also low, which indicates that the loss of iron ions is high, and the purpose of ensuring high yield of iron phosphate while deeply removing aluminum is not achieved.
As can be seen from the results of example 4 and comparative example 2, salicylic acid is used as an aluminum remover in the step of comparative example 2, and although the yield of the iron phosphate is slightly improved, most of aluminum impurities in the iron phosphate cannot be removed, so that the aim of deep aluminum removal in the invention is not achieved.
As can be seen from the results of example 4 and comparative example 3, in the step of comparative example 3, EDTA was used as an aluminum remover, most of aluminum impurities could not be removed, the purpose of deep aluminum removal of the present invention was not achieved, and the yield and purity of iron phosphate were greatly reduced.
As can be seen from the results of example 4 and comparative example 4, HEDP is used as an aluminum remover in the step of comparative example 4, most of aluminum impurities cannot be removed, the aim of deep aluminum removal in the invention is also fulfilled, and the yield and purity of the iron phosphate are greatly reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The aluminum removing method of the phosphorus-iron slag after lithium extraction of waste lithium iron phosphate is characterized by comprising the following steps of:
mixing the ferrophosphorus slag obtained after lithium extraction of waste lithium iron phosphate, an iron simple substance, acid and water, and carrying out acid leaching reaction to obtain slurry A;
mixing the slurry A with an aluminum remover to perform aluminum removal reaction, and then removing solids to obtain a phosphorus iron liquid after aluminum removal;
the aluminum remover is at least one selected from picolinic acid compounds, quinolinecarboxylic acid compounds and isoquinoline-3-carboxylic acid compounds.
2. The method for removing aluminum from the phosphorus-iron slag after lithium extraction by the waste lithium iron phosphate according to claim 1, wherein the picolinic acid compound is selected from 2-picolinic acid, 3-phenyl-2-picolinic acid, 2-picolinic acid methyl ester, 2-picolinic acid ethyl ester, 2-picolinic acid propyl ester or 2-picolinic acid butyl ester; and/or
The quinoline carboxylic acid compound is selected from 2-quinoline carboxylic acid, 2-quinoline carboxylic acid methyl ester, 2-quinoline carboxylic acid ethyl ester, 2-quinoline carboxylic acid propyl ester or 2-quinoline carboxylic acid butyl ester; and/or
The isoquinoline-3-formic acid compound is selected from isoquinoline-3-formic acid, isoquinoline-3-methyl formate, isoquinoline-3-ethyl formate, isoquinoline-3-propyl formate or isoquinoline-3-butyl formate.
3. The method for removing aluminum from the phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate as claimed in claim 1, wherein the mass ratio of the aluminum remover to the phosphorus-iron slag after lithium extraction from the waste lithium iron phosphate is (0.01-0.1): 1; and/or
The mass ratio of the iron simple substance to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.15-0.35): 1.
4. the method for removing aluminum from the ferrophosphorus slag after extracting lithium from waste lithium iron phosphate according to claim 1, wherein the acid is at least one selected from hydrochloric acid, sulfuric acid and phosphoric acid; and/or
The mass ratio of the acid to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.5-1.5): 1.
5. the method for removing aluminum from the ferrophosphorus slag after extracting lithium from waste lithium iron phosphate according to any one of claims 1 to 4, wherein the solid-to-liquid ratio of the slurry A is 20g/L to 150 g/L.
6. The method for removing aluminum from the ferrophosphorus slag after extracting lithium from waste lithium iron phosphate according to any one of claims 1 to 4, wherein the parameters of the acid leaching reaction comprise:
the reaction temperature is 40-80 ℃, and the reaction time is more than or equal to 4 hours.
7. The method for removing aluminum from the ferrophosphorus slag after extracting lithium from waste lithium iron phosphate according to any one of claims 1 to 4, wherein the parameters of the aluminum removal reaction comprise:
the reaction temperature is 50-100 ℃, and the reaction time is more than or equal to 2 hours; and/or
The aluminum removal reaction is carried out in an inert gas, carbon dioxide or nitrogen atmosphere.
8. A preparation method of battery-grade iron phosphate is characterized by comprising the following steps:
the ferrophosphorus liquid is prepared by the aluminum removing method of the ferrophosphorus slag after extracting lithium from the waste lithium iron phosphate according to any one of claims 1 to 7;
and mixing the ferrophosphorus solution with an oxidant and a pH regulator to perform an oxidation reaction.
9. The method of claim 8, wherein the oxidant is selected from at least one of hydrogen peroxide, air, ozone, or oxygen, and/or
The pH regulator is at least one selected from ammonia water, ammonium carbonate or ammonium bicarbonate.
10. The preparation method of the battery-grade iron phosphate according to claim 9, wherein the mass ratio of the oxidant to the phosphorus-iron slag obtained after lithium extraction from the waste lithium iron phosphate is (0.3-0.9): 1; and/or
The parameters of the oxidation reaction include: the reaction temperature is 40-100 ℃, the reaction time is more than or equal to 4 hours, and the pH value of the reaction system is 1.5-2; and/or
After the oxidation reaction is finished, filtering, washing and drying treatment are also carried out.
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